聚乙烯吡咯烷酮辅助金属有机框架衍生分级多孔碳材料的制备及其双功能催化性能研究

doi:10.6023/A25060236

摘要/Abstract

双效氧电极中的氧还原反应(ORR)和析氧反应(OER)是众多电化学储能技术的基石, 包括燃料电池、水电解等. 然而, ORR/OER过程均涉及多步质子/电子耦合传递, 导致氧电极反应动力学缓慢且需要施加高活化过电位才可发生, 因此探寻合适的电催化剂以降低反应势垒和加快电子传输是提高能量转化效率的关键. 本工作报道了一种双金属协同催化与界面工程耦合调控策略, 该策略可通过聚乙烯吡咯烷酮(PVP)辅助热解将Co/Ni双金属有机框架(MOF)前驱体转化为钴镍合金纳米粒子嵌入的分级多孔碳材料(P-CoNi-N-C). 实验结果显示: P-CoNi-N-C具有几乎接近于Pt/C的ORR性能(起始电位为1.053 V, 半波电位为0.825 V, 电子转移数为3.96)和出色的OER性能(E_j₌₁₀为1.609 V, 过电位为0.379 V, 1.60 V电势下P-CoNi-N-C的质量活性为Co-N-C的5倍). 同样地, P-CoNi-N-C具有优异的长期稳定性, 其电流衰减率仅为0.84%•h^-1. 表征结果验证了P-CoNi-N-C优异的双功能活性源于其分级多孔结构、优化中间体吸附能和独特的异质界面结构的协同作用. 此外, P-CoNi-N-C催化剂在可充电锌空气电池展现出优异的电化学性能(充电电流密度为127 mA•cm^-2, 功率密度为127.3 mW•cm^-2)和循环稳定性(80 h后容量保持率为92%).

关键词: 氧还原反应, 析氧反应, 金属有机框架, 分级多孔, 异质界面结构

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring at bifunctional oxygen electrodes are fundamental to numerous electrochemical energy storage and conversion technologies, including fuel cells and water electrolysis. However, both ORR and OER involve multi-step proton-coupled electron transfers, resulting in sluggish reaction kinetics and requiring high activation overpotentials. Consequently, developing efficient electrocatalysts to lower the reaction energy barriers and accelerate electron transfer is critical for enhancing energy conversion efficiency. This work presents a synergistic strategy integrating bimetallic catalysis with interface engineering. Specifically, a cobalt/nickel bimetallic metal-organic framework (MOF) precursor undergoes polyvinylpyrrolidone (PVP)-assisted pyrolysis, transforming into a hierarchically porous nitrogen-doped carbon matrix embedded with cobalt-nickel alloy nanoparticles (P-CoNi-N-C). Electrochemical characterization reveals that P-CoNi-N-C exhibits ORR performance rivaling commercial Pt/C (onset potential of 1.053 V, half-wave potential of 0.825 V, and electron transfer number of 3.96) and exceptional OER activity (E_j₌₁₀ of 1.609 V, low overpotential of 0.379 V, and mass activity of P-CoNi-N-C at 1.60 V is five times that of Co-N-C). Similarly, P-CoNi-N-C has remarkable long-term stability with a current attenuation rate of only 0.84%•h^-1. Comprehensive material characterization confirms that the superior bifunctional performance of P-CoNi-N-C stems from the synergistic interplay of its hierarchically porous architecture, optimized adsorption energy for oxygen intermediates, and unique heterointerface structure. Furthermore, the P-CoNi-N-C catalyst exhibits excellent electrochemical performance (charge current density of 127 mA•cm^-2 and power density of 127.3 mW•cm^-2) and cycling stability (capacity retention rate of 92% after 80 h) in rechargeable zinc-air batteries.

Key words: oxygen reduction reactions, oxygen evolution reaction, metal-organic frameworks, graded porous, heterogeneous interfacial structure

引用此文

税子怡, 尹书睿, 邓锦涛, 许留云, 郭莉. 聚乙烯吡咯烷酮辅助金属有机框架衍生分级多孔碳材料的制备及其双功能催化性能研究[J]. 化学学报, 2026, 84(1): 53-63.

Ziyi Shui, Shurui Yin, Jintao Deng, Liuyun Xu, Li Guo. Polyvinylpyrrolidone-Assisted Synthesis of Metal-organic Framework-Derived Hierarchically Porous Carbon for Bifunctional Electrocatalysis[J]. Acta Chimica Sinica, 2026, 84(1): 53-63.

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图/表 11

图1. (a) Co-N-C和(b) P-CoNi-N-C的合成示意图

Figure 1. Synthesis schema of (a) Co-N-C and (b) P-CoNi-N-C

图2. (a) ZIF-67和(b) Co-N-C催化剂, (c) P-ZIF-67和(d) P-Co-N-C催化剂的SEM图像; P-Co-N-C的(e) TEM图像, (f) HRTEM图像, (g) SAED图案和(h) EDS元素分布图

Figure 2. SEM images of (a) ZIF-67 and (b) Co-N-C catalysts, (c) P-ZIF-67 and (d) P-Co-N-C catalysts; (e) TEM image, (f) HRTEM image, (g) SAED pattern and (h) EDS elemental distribution mappings of P-Co-N-C

图3. (a) P-Ni-ZIF-67和(b) P-CoNi-N-C催化剂的SEM图像; P-CoNi-N-C的(c) TEM图像, (d) HRTEM图像, (e) SAED图案和(f) EDS元素分布图

Figure 3. SEM images of (a) P-Ni-ZIF-67 and (b) P-CoNi-N-C catalysts; (c) TEM image, (d) HRTEM image, (e) SAED pattern and (f) EDS elemental distribution mappings of P-CoNi-N-C

图4. Co-N-C, P-Co-N-C和P-CoNi-N-C催化剂的(a) XRD图谱, (b) N2吸附等温线, (c)热重分析曲线和(d)拉曼光谱

Figure 4. (a) XRD patterns, (b) N2 adsorption/desorption curves, (c) Raman spectra, (d) TGA curves of Co-N-C, P-Co-N-C and P-CoNi-N-C catalysts

图5. Co-N-C, P-Co-N-C和P-CoNi-N-C的高分辨率(a) N 1s光谱, (b) Co 2p光谱和(c) C 1s光谱

Figure 5. High-resolution (a) N 1s spectra, (b) Co 2p spectra and (c) and C 1s spectra of Co-N-C, P-Co-N-C and P-CoNi-N-C

	S_BET/ (m²•g^-1)	S_Micro/ (m²•g^-1)	S_Meso/ (m²•g^-1)	V_Pore/ (cm³•g^-1)
Co-N-C	188	46	142	0.19
P-Co-N-C	285	54	231	0.32
P-CoNi-N-C	296	58	238	0.34

表1. 多孔特性总结

Table 1. Summary of the porous properties

图6. Co-N-C, P-Co-N-C, P-CoNi-N-C和Pt/C催化剂的(a)氧还原极化曲线, (b)催化剂上收集的Eonset和E1/2, (c)塔菲尔图和(d)通过计时安培技术测量的ORR稳定性

Figure 6. (a) Oxygen reduction polarization curve, (b) Eonset and E1/2 collected on catalysts, (c) Tafel plot and (d) ORR stability measured by chronoamperometric technique of Co-N-C, P-Co-N-C, P-CoNi-N-C and Pt/C catalysts

图7. (a) Co-N-C, (b) P-Co-N-C, (c) P-CoNi-N-C和(d) Pt/C催化剂在不同转速下的ORR极化曲线和Koutecky-Levich图; 四种催化材料在(e) 0.2~0.8 V范围内的电子转移数及(f) 0.4 V时相应动电流密度图

Figure 7. ORR polarization curves at various speeds and the Koutecky-Levich plots of (a) Co-N-C, (b) P-Co-N-C, (c) P-CoNi-N-C and (d) Pt/C catalysts; (e) The electron transfer numbers in the range of 0.2~0.8 V and (f) the corresponding kinetic current density at 0.4 V of four catalytic materials

图8. Co-N-C, P-Co-N-C, P-CoNi-N-C和RuO2催化剂的(a)析氧极化曲线, (b)塔菲尔图, (c)质量活性对比, (d)由电化学活性表面积(ECSA)确定的双层电容值(Cdl), (e) EIS图和(f)通过计时安培法技术测试的OER稳定性

Figure 8. (a) Oxygen evolution polarization curve; (b) Tafel plot; (c) Mass-activity comparison, (d) double-layer capacitance (Cdl) as determined by electrochemically active surface area (ECSA), (e) EIS plot and (f) OER stability measured by chronoamperometric technique of Co-N-C, P-Co-N-C, P-CoNi-N-C and RuO2 catalysts

图9. 在ORR/OER电位窗口下Co-N-C, P-Co-N-C, P-CoNi-N-C, Pt/C和RuO2催化剂的双功能特性

Figure 9. Bifunctional property of Co-N-C, P-Co-N-C, P-CoNi-N-C, Pt/C and RuO2 catalysts at ORR/OER potential window

图10. (a)可充电锌空气电池示意图; (b)充放电极化曲线及(c)其相应的放电功率密度曲线; (d)恒流充放电循环稳定性测试

Figure 10. (a) Diagram of rechargeable zinc air battery, (b) Charge-discharge polarization curve and (c) its corresponding discharge power density curve, (d) Constant current charge-discharge cycle stability test

参考文献 31

[1]	Qiu, D.; Wang, H.; Ma, T.; Huang, J.; Meng, Z.; Fan, D.; Bowen, C. R.; Lu, H.; Liu, Y.; Chandrasekaran, S. ACS Nano 2024, 18, 21651. doi: 10.1021/acsnano.4c02289
[2]	Duan, N.; Wang, J, Wang R, Han, G.; Wu, X.; Liu, Y.; Li, B. Adv. Sustain. Syst. 2025, 9, 2400881. doi: 10.1002/adsu.v9.3
[3]	Song, Y.; Li, W.; Zhang, K.; Han, C.; Pan, A. Adv. Energy Mater. 2024, 14, 2303352. doi: 10.1002/aenm.v14.7
[4]	Shui, Z.; Yu, S.; Lu, W.; Xu, L.; Liu, Q.; Zhao, W.; Liu, Y. Acta Chim. Sinica 2024, 82, 1039. (in Chinese) doi: 10.6023/A24050152
	(税子怡, 于思乐, 陆伟, 许留云, 刘庆叶, 赵炜, 刘益伦, 化学学报, 2024, 82, 1039.) doi: 10.6023/A24050152
[5]	Humayun, M.; Li, Z.; Israr, M.; Khan, A.; Luo, W.; Wang, C.; Shao, Z. Chem. Rev. 2025, 125, 3165. doi: 10.1021/acs.chemrev.4c00553
[6]	Li, H.; Yan, G.; Zhao, H.; Howlett, P. C.; Wang, X.; Fang, J. Adv. Mater. 2024, 36, 2311272. doi: 10.1002/adma.v36.26
[7]	Liu, Y.; Zhou, L.; Liu, S.; Li, S.; Zhou, J.; Li, X.; Chen, X.; Sun, K.; Li, B.; Jiang, J.; Pang, H. Angew. Chem. Int. Ed. 2024, 63, e202319983. doi: 10.1002/anie.v63.16
[8]	Wang, Y.; Wang, M.; Li, J.; Wei, Z. Acta Chim. Sinica 2019, 77, 84. (in Chinese) doi: 10.6023/A18080357
	(王艺霖, 王敏杰, 李静, 魏子栋, 化学学报, 2019, 77, 84.) doi: 10.6023/A18080357
[9]	Wu, X.; Yang, Z.; Li, C.; Shao, S.; Qin, G.; Meng, X. ACS Catal. 2025, 15, 432. doi: 10.1021/acscatal.4c06280
[10]	Wang, F.; He, X.; Qu, G.; Mamoor, M.; Zhai, Y.; Wang, L.; Wang, B.; Jing, Z.; Kong, Y.; Wang, D.; Kong, L.; Xu, L. ACS Nano 2025, 19, 22330. doi: 10.1021/acsnano.5c05171
[11]	Kim, D. W.; Choi, J. H.; Cho, S.; Kim, K.-H.; Kang J. K. ACS Appl. Mater. Interfaces 2025, 17, 32469. doi: 10.1021/acsami.5c04851
[12]	Li, R.-J.; Niu, W.-J.; Zhao, W.-W.; Yu, B.-X.; Cai, C.-Y.; Xu, L.-Y.; Wang, F.-M. Small 2025, 21, 2408227. doi: 10.1002/smll.v21.1
[13]	Tang, J.; Salunkhe, R. R.; Liu, J.; Torad, N. L.; Imura, M.; Furukawa, S.; Yamauchi, Y. J. Am. Chem. Soc. 2015, 137, 1572. doi: 10.1021/ja511539a
[14]	Kuang, M.; Wang, Q.; Han, P.; Li, N.; Xu, Q.; Li, H.; He, J.; Lu, J. Adv. Energy Mater. 2017, 7, 1700193. doi: 10.1002/aenm.v7.17
[15]	Tang, J.; Yamauchi, Y. Nat. Chem. 2016, 8, 638. doi: 10.1038/nchem.2548
[16]	Yan, S.; Jiao, L.; He, C.; Jiang, H. Acta Chim. Sinica 2022, 80, 1084. (in Chinese) doi: 10.6023/A22040143
	(闫绍兵, 焦龙, 何传新, 江海龙, 化学学报, 2022, 80, 1084.) doi: 10.6023/A22040143
[17]	Liu, J.; Sun, Q.; Ye, Q.; Chen, J.; Wu, Y.; Ge, Y.; Zhang, L.; Yang, Z.; Qian, J. ACS Sustain. Chem. Eng. 2024, 12, 4779. doi: 10.1021/acssuschemeng.4c00459
[18]	Pachfule, P.; Shined, D.; Majumder, M.; Xu, Q. Nat. Chem. 2016, 8, 718. doi: 10.1038/nchem.2515 pmid: 27325100
[19]	Meng, J.; Niu, C.; Xu, L.; Li, J.; Liu, X.; Wang, X.; Wu, Y.; Xu, X.; Chen, W.; Li, Q.; Zhu, Z.; Zhao, D.; Mai, L. J. Am. Chem. Soc. 2017, 139, 8212. doi: 10.1021/jacs.7b01942
[20]	Liu, J.; Ou, J.; Li, Z.; Jiang, J.; Liang, R.; Zhang, W.; Liu, K.; Han, Y. Acta Chim. Sinica 2023, 81, 1701. (in Chinese) doi: 10.6023/A23080374
	(刘健, 欧金花, 李泽平, 蒋婧怡, 梁荣涛, 张文杰, 刘开建, 韩瑜, 化学学报, 2023, 81, 1701.) doi: 10.6023/A23080374
[21]	Lin, X.; Lin, D.; Zhang, W.; Liu, J.; Shen, Y.; Qian, J. Front. Energy 2025, DOI: 10.1007/s11708-025-1001-9.
[22]	Amali, A. J.; Sun, J.-K.; Xu, Q. Chem. Commun. 2014, 50, 1519. doi: 10.1039/C3CC48112C
[23]	Li, X.; Sun, Q.; Liu, J.; Xiao, B.; Li, R.; Sun, X. J. Power Sources 2016, 302, 174. doi: 10.1016/j.jpowsour.2015.10.049
[24]	Liang, Z.; Zhang, C.; Yuan, H.; Zhang, W.; Zheng, H.; Cao, R. Chem. Commun. 2018, 54, 7519. doi: 10.1039/C8CC02646G
[25]	Lai, Q.; Zhao, Y.; Liang, Y.; He, J.; Chen, J. Adv. Funct. Mater. 2016, 26, 8334. doi: 10.1002/adfm.v26.45
[26]	Zhang, M.; Dai, Q.; Zheng, H.; Chen, M.; Dai, L. Adv. Mater. 2018, 30, 1705431. doi: 10.1002/adma.v30.10
[27]	Guo, D.; Chen, F.; Zhang, W.; Cao, R. Sci. Bull. 2017, 62, 626. doi: 10.1016/j.scib.2017.03.027
[28]	Zhuang, Q.; Ma, N.; Yin, Z.; Yang, X.; Yin, Z.; Gao, J.; Xu, Y.; Gao, Z.; Wang, H.; Kang, J.; Xiao, D.; Li, J.; Li, X.; Ma, D. Adv. Energy Sustain. Res. 2021, 2, 2100030. doi: 10.1002/aesr.v2.8
[29]	Wang, X.-T.; Ouyang, T.; Wang, L.; Zhong, J.-H.; Liu, Z.-Q. Angew. Chem. Int. Ed. 2020, 59, 6492. doi: 10.1002/anie.v59.16
[30]	Wang, Y.; Liu, J.; Xu, N.; Li, S.; Zhang, H.; Luo, X.; Wang, Z.; Cui, X.; Qiao, J. ChemCatChem 2025, 17, e00731. doi: 10.1002/cctc.v17.16
[31]	Wang, X.; Pan, Z.; Chu, X.; Huang, K.; Cong, Y.; Cao, R.; Sarangi, R.; Li, L.; Li, G.; Feng, S. Angew. Chem. Int. Ed. 2019, 58, 11720. doi: 10.1002/anie.v58.34